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<ul><li><p>MDI and TDI: Safety, Healthand the Environment.A Source Book and Practical Guide</p><p>Edited by:</p><p>D C AllportGilbert International Ltd, Manchester, UK</p><p>D S GilbertGilbert International Ltd, Manchester, UK</p><p>and</p><p>S M OuttersideGilbert International Ltd, Manchester, UK</p></li><li><p>MDI and TDI: Safety, Healthand the Environment.A Source Book and Practical Guide</p></li><li><p>MDI and TDI: Safety, Healthand the Environment.A Source Book and Practical Guide</p><p>Edited by:</p><p>D C AllportGilbert International Ltd, Manchester, UK</p><p>D S GilbertGilbert International Ltd, Manchester, UK</p><p>and</p><p>S M OuttersideGilbert International Ltd, Manchester, UK</p></li><li><p>Copyright 2003 John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester,West Sussex PO19 8SQ, England</p><p>Telephone (+44) 1243 779777Email (for orders and customer service enquiries): [email protected] our Home Page on www.wileyeurope.com or www.wiley.com</p><p>All Rights Reserved. No part of this publication may be reproduced, stored in a retrieval system ortransmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanningor otherwise, except under the terms of the Copyright, Designs and Patents Act 1988 or under theterms of a licence issued by the Copyright Licensing Agency Ltd, 90 Tottenham Court Road,London W1T 4LP, UK, without the permission in writing of the Publisher. Requests to the Publishershould be addressed to the Permissions Department, John Wiley & Sons Ltd, The Atrium, SouthernGate, Chichester, West Sussex PO19 8SQ, England, or emailed to [email protected], or faxed to(+44) 1243 770620.This publication is designed to provide accurate and authoritative information in regard to the subjectmatter covered. It is sold on the understanding that the Publisher is not engaged in renderingprofessional services. If professional advice or other expert assistance is required, the services of acompetent professional should be sought.</p><p>Other Wiley Editorial Offices</p><p>John Wiley & Sons Inc., 111 River Street, Hoboken, NJ 07030, USA</p><p>Jossey-Bass, 989 Market Street, San Francisco, CA 94103-1741, USA</p><p>Wiley-VCH Verlag GmbH, Boschstr. 12, D-69469 Weinheim, Germany</p><p>John Wiley & Sons Australia Ltd, 33 Park Road, Milton, Queensland 4064, Australia</p><p>John Wiley & Sons (Asia) Pte Ltd, 2 Clementi Loop #02-01, Jin Xing Distripark, Singapore 129809</p><p>John Wiley & Sons Canada Ltd, 22 Worcester Road, Etobicoke, Ontario, Canada M9W 1L1</p><p>Library of Congress Cataloging-in-Publication Data</p><p>MDI and TDI : safety, health and the environment. A source book and practical guide / edited byD.C. Allport, D.S. Gilbert, and S.M. Outterside.</p><p>p. cm.Includes bibliographical references and index.ISBN 0-471-95812-3 (alk. paper)1. Isocyanates Safety measures. 2. Methylenediphenyl diisocyanate Safety measures. 3.</p><p>Toluene diisocyanate Safety measures. I. Allport, Dennis C. II. Gilbert, D. S. III.Outterside, S. M.</p><p>TP248.I8 M45 2002668.42390289dc21 2002033117</p><p>British Library Cataloguing in Publication Data</p><p>A catalogue record for this book is available from the British Library</p><p>ISBN 0-471-95812-3</p><p>Typeset in 10.5/12.5pt Times by Laserwords Private Limited, Chennai, IndiaPrinted and bound in Italy by Conti TipcolorThis book is printed on acid-free paper responsibly manufactured from sustainable forestry in whichat least two trees are planted for each one used for paper production.</p><p>While the International Isocyanate Institute (III) has supported the preparation of this text,the views expressed therein are those of the authors and not necessarily those of the III or itsmembers. While great care has been taken in the preparation and editing of this text, neitherthe III, its members, nor the authors or editors of this text can accept responsibility for anyerrors or omissions therein. While the text discusses certain of the manufacturing, handling,environmental, medical and other aspects of the diisocyanate industry, it does not purport tobe, and is not, a comprehensive guide thereto.</p></li><li><p>Contents</p><p>List of authors and affiliations ixA book of distinction xvAcknowledgements xvii</p><p>Part PageMDI and TDI usage: responsible riskmanagement 1D C Allport, D S Gilbert andS M Outterside</p><p>Exposure, hazard and risk 1Responsible Care: a frameworkfor industry action 5Reading 10</p><p>1 MDI, TDI and the polyurethaneindustry 11D C Allport, D S Gilbert andS M Outterside</p><p>Types of MDI 13Types of TDI 15Test substances 16Misapprehensions 16Polyurethanes made from MDI andTDI 17Reading 23</p><p>2 Handling MDI and TDI 25D C Allport, R C Blake, C Bastian,C Galavitz, D S Gilbert, R Hurd,B Reeve, W Robert, S M Outterside,A Solinas, D Walsh, U Walber andH Wolfson</p><p>Pride in safety 25Successful systems 25Safety systems for thehandling of MDI and TDI 26</p><p>Part PageKey Theme 1: Know your product</p><p>Health 31Environment 32</p><p>Key Theme 2: Protecting health 33Duty of care 33Exposure: how can MDI orTDI enter the body? 34Medical symptoms 35Medical checks 36</p><p>Key Theme 3: Neutralization,decontamination and disposal ofwastes</p><p>Types of neutralizer 40Routine cleaning ofequipment and drums 40Neutralization after a spillage 43Neutralizer formulations 46</p><p>Key Theme 4: Using personalprotective equipment 47</p><p>Normal operations 47Emergency situations 48Selection of personalprotective equipment 49Protective clothing 50Respiratory protection 51</p><p>Key Theme 5: Monitoring exposure 59How should monitoring becarried out? 60When should monitoring becarried out? 61</p><p>Key Theme 6: Dealing withaccidents 62</p><p>Accidents can happen 62Spillages 63Development of excesspressure inside containers 68Incidents involving fire 70</p><p>2</p><p>39</p><p>9</p></li><li><p>vi Contents</p><p>Part PageTransport of MDI and TDI 72</p><p>Transport regulations 73MDI and TDI: transporttemperaturesTypical containers for thetransport of diisocyanates 75Accidents and emergencies 85</p><p>The workplace: storage and use ofMDI and TDI 86</p><p>Designing the systems andminimizing the risks 87Physical and chemicalproperties relating to storageand processing 93Storage of MDI and TDI 95Safety issues in workplacesusing MDI and TDI 106Safety issues in someimportant polyurethaneprocesses 117Use of MDI and TDI inlaboratories 122Visitors to the workplace 123Emergencies in the workplace 124</p><p>Releases to atmosphere frompolyurethane manufacturing sites 126</p><p>Properties of MDI and TDIrelevant to releasesto atmosphere 127Releases from polyurethaneprocessesAbatement of releases</p><p>Reading</p><p>3 Health 155D C Allport, P Davies, W F Diller,J E Doe, F Floch, H D Hoffmann,M Katoh and J P Lyon. Appendices byD I Bernstein</p><p>Perspective on immediate effectsfollowing over-exposure 156First aid procedures 156</p><p>Commentary on first aidprocedures 157</p><p>Human health: the medicalbackground 160</p><p>Effects on the eyes 163Effects on the skin 163</p><p>Part PageEffects when swallowed 165Effects on the respiratory tract 165Other health effects of MDIand TDI 185Biomonitoring of MDIand TDI 186</p><p>Experimental toxicology 187The interaction of MDI andTDI with biological systems 188Toxicology studies 193</p><p>Diagnosis of diisocyanateasthma 203Appendices (David I. Bernstein) 203Reading 217</p><p>4 The environment 229R E Bailey, A Gard, K H den Haan,F Heimbach, D Pemberton, H Tadokoro,M Takatsuki and Y Yakabe</p><p>A general approach toenvironmental risk assessment 229Exposure 233</p><p>Sources of exposure 233Distribution andpersistence 237Biodegradation 256Bioaccumulation 257</p><p>Hazard 258Test procedures 258Aquatic ecotoxicity 259Terrestrial ecotoxicity 264</p><p>Risk assessment 265Accidental release of MDIand TDI 266Normal usage 268</p><p>Reading 2735 Supporting sciences 277</p><p>5.1 Chemistry of manufacture of MDIand TDI 277D C Allport, D S Gilbert andB Tury</p><p>Manufacture of MDI 277Manufacture of TDI 280Modified MDI and TDI 282</p><p>Reading 2845.2 Structures and nomenclature 285</p><p>D C Allport, D S Gilbert andB Tury</p><p>7</p><p>148</p><p>4</p><p>12138</p><p>8</p></li><li><p>Contents vii</p><p>Part PageStructures 285CAS Registry numbers andpreferred names 286IUPAC names 287Convenient names for MDIand TDI 288Synonyms 289Commercial product names 289Reading 291</p><p>5.3 Chemical reactions of MDIand TDI 291D C Allport, D S Gilbert,D Pemberton and B Tury</p><p>Reaction with OH groups 292Reaction with NH groups 293Reaction with SH groups 293Reaction with biologicalmolecules 294Self-reactions 295Catalysts 298</p><p>Reading 2995.4 Physical and fire properties 300</p><p>S M Outterside and D PembertonMDI 301TDI 311</p><p>Reading 3205.5 Fire behaviour of MDI and TDI 321</p><p>J F Chapman, B Cope, G Marlairand F Prager</p><p>Part PageTest methodology 321Fire tests on MDI and TDI 323</p><p>Reading 3405.6 Occupational exposure limits, stack</p><p>limits and community limits 343D C Allport, D S Gilbert,S M Outterside and B Tury</p><p>Occupational exposure limits 343Stack release limits andcommunity limits 351</p><p>Reading 3585.7 Sampling and analysis 358</p><p>K S Brenner, V Dharmarajan andP Maddison</p><p>Materials to be measured 358Airborne MDI and TDIspecies 359Choice of methods for thesampling and analysis of MDIand TDI in air 361Analysis of nonairborne MDIand TDI 418A critical review of exposureassessment techniques used inoccupational health studies ofMDI and TDI 421</p><p>Reading 423</p><p>Index 431</p></li><li><p>List of authors and affiliations</p><p>Affiliation to International Isocyanate Institute (III)</p><p>Dennis C AllportGilbert International LimitedIII Scientific Office, Manchester, UK(Formerly with ICI, Manchester, UK and Everberg, Belgium)III Scientific Committee (Chairman)III Health Advisory Group</p><p>Robert E BaileyBailey AssociatesMidlandMichigan, USA(Formerly with Dow, Midland, USA)III Environmental Advisory GroupIII Americas Environmental Committee</p><p>Claude BastianDow Europe S.A.Horgen, SwitzerlandIII Scientific CommitteeIII Environmental Advisory Group (Chairman)III European Environmental Committee (Chairman)</p><p>David I BernsteinAssociate Professor of MedicineUniversity of Cincinnati, USA</p><p>R C BlakeBayer CorporationPittsburgh, USAIII Americas Handling Committee (Chairman)</p><p>Karl S BrennerConsulting Analytical & Technical SupportLu-Oggersheim, Germany(Formerly with BASF, Ludwigshafen, Germany)III European Analytical Committee (Chairman)III Analytical Advisory Group</p></li><li><p>x List of authors and affiliations</p><p>John F ChapmanGilbert International LimitedIII Scientific Office, Manchester, UK(Formerly with ICI and BRUFMA, both Manchester, UK)III Analytical Advisory Group</p><p>Brian CopeGilbert International LimitedIII Scientific Office, Manchester, UK(Formerly with Shell, Louvain, Belgium)III European Combustibility Committee (Chairman)</p><p>Peter DaviesHuntsman PolyurethanesEverberg, BelgiumIII Scientific CommitteeIII Health Advisory Group (Chairman)III European Medtox Committee</p><p>Venkatram DharmarajanBayer CorporationPittsburgh, USAIII Americas Analytical Committee</p><p>Werner F DillerHeinrich Heine UniversityGermany(Formerly with Bayer, Leverkusen, Germany)III European Medtox Committee (Chairman)III Health Advisory Group</p><p>John DoeSyngenta Central Toxicology LaboratoriesMacclesfield, UKIII Health Advisory Group (Chairman)III European Medtox Committee (Chairman)</p><p>Francois E FlochRhodiaSaint-Fons, FranceIII European Medtox Committee</p><p>Charles GalavitzDow Chemical CompanyTexas, USAIII Americas Handling Committee</p><p>Arielle GardRhodiaSaint-Fons, FranceIII Environmental Advisory GroupIII European Environmental Group</p></li><li><p>List of authors and affiliations xi</p><p>David S GilbertInternational Isocyanate Institute IncGilbert International LimitedIII Scientific Office, Manchester, UK(Formerly with ICI, Manchester, UK)III Scientific DirectorIII Environmental Advisory GroupIII Fire Science Task ForceIII Product Safety Advisory GroupIII Phosgene Safety Task Force</p><p>Klaas H den HaanShell International ChemicalsShell Research & Technology CentreAmsterdam, The NetherlandsIII Environmental Advisory Group</p><p>Hans D HoffmannBASF AktiengesellschaftDepartment of ToxicologyLudwigshafen, GermanyIII Scientific CommitteeIII Health Advisory Group (Chairman)III European Medtox Committee (Chairman)III Biochemistry Task Force (Chairman)</p><p>Reg HurdWindley, DerbyshireUK(Formerly with ICI, Manchester, UK and with Europur, Brussels, Belgium)III Scientific Committee (Chairman)</p><p>Masabaru KatohMitsubishi Chemical Safety InstituteTokyo, JapanIII Health Advisory GroupIII Asia Pacific Medtox Group</p><p>James P LyonHuntsman PolyurethanesWest Deptford, USAIII Scientific CommitteeIII Health Advisory Group (Chairman)III Product Safety Advisory Group (Chairman)</p><p>Paul MaddisonHuntsman PolyurethanesEverberg, BelgiumIII Scientific CommitteeIII European Analytical Committee (Chairman)III Analytical Advisory Group (Chairman)</p></li><li><p>xii List of authors and affiliations</p><p>Guy MarlairINERISVerneuil-en-Halatte, France</p><p>Susan M OuttersideGilbert International LimitedIII Scientific Office, Manchester, UK</p><p>Denis PembertonGilbert International LimitedIII Scientific Office, Manchester, UK</p><p>Franz H PragerLeverkusen, Germany(Formerly of Bayer, AG, Germany)III European Combustibility Committee (Chairman)</p><p>Brian ReeveTeddingtonMiddlesex, London, UK(Formerly with Shell, London, UK)III Scientific Committee</p><p>William RobertBASF CorporationWyandotteMichigan, USAIII Americas Handling Committee (Chairman)III Americas Environmental GroupIII Issues Coordinating Group</p><p>Anthony SolinasLyondellHouston, Texas, USAIII Americas Handling Committee (Chairman)</p><p>Hiroshi TadokoroChemicals Inspection and Testing InstituteKurume, Japan</p><p>Mineo TakatsukiChemicals Inspection and Testing InstituteTokyo, Japan</p><p>Bernard TuryGilbert International LimitedIII Scientific Office, Manchester, UK</p></li><li><p>List of authors and affiliations xiii</p><p>Udo WalberBayer AGLeverkusen, GermanyIII European Medtox CommitteeIII Product Safety Advisory GroupIII European Environmental Group</p><p>John D WalkerTSCA Interagency Testing CommitteeEnvironmental Protection Agency (7401)Washington DC, USA</p><p>Dale WalshRubicon Inc/HuntsmanLouisiana, USAIII Americas Handling Committee</p><p>Hugh WolfsonPrincipal Specialist Inspector (Chemical)Health and Safety ExecutiveManchester, UK</p><p>Yoshikuni YakabeManager, Research DepartmentChemicals Inspection and Testing InstituteKurume, Japan</p><p>The III Scientific Office, Bridgewater House Floor 9, Whitworth Street,Manchester M1 6LT, UK is operated by Gilbert International Limited, aprivate contractor.</p></li><li><p>A book of distinction</p><p>International Isocyanate Institute Inc. sponsorship</p><p>The International Isocyanate Institute Inc. (III) was founded in August 1972,as a non-profit corporation, in order to promote and further the interests ofthe public, the users and the manufacturers of MDI and TDI in the handlingof these diisocyanates. For almost three decades it has devoted considerablefunding, and the services of many experts in a wide range of disciplines, tothe study of all aspects of the safe handling of MDI and TDI. These studieshave been conducted with great energy and perseverance. It was my privilegeas the then President of III to chair the meeting in which it was decided tosupport the preparation of this book, to allow our findings to be communicatedto a wide audience and, above all, to translate our knowledge into a detailedguide on safe handling techniques.</p><p>Global perspective</p><p>III is a global industry research institute. Member companies operate plantsin North America, South America, Europe and the Asia Pacific regions. TheInstitute supports a wide diversity of advisory groups and task forc..</p></li></ul>